Alkynyl alcohols

ABSTRACT

Aliphatic substituted allenic and diolefinic esters, intermediates therefor, derivatives thereof and the control of insects.

Unlted States Patent l I I I 3,91 1,025

Henrick el al. Oct. 7, 1975 ALKYNYL ALCOHOLS [5 I] Int. Cl. t. C07C 43/00; C07C 43/l4 [75] Inventors: Clive Hamid; John Sidda", [58] Fleld of Search 0. 260/615 R both of P2110 Alto, Calif.

[56] References Cited [73} Assignee: Zoecon Corporation, Pulo Alto,

Cant OTHER PUBLICATIONS j [22] Filed: Jan. 7, 1974 Gdrievz et al, Chem Abs 67 32287 y (1967).

[Zl] Appl. No.: 431,522 Primary ExaminerHoward T. Mars Re'med Applicafion Data Attorney, Agent, or FirmD0nald W. Erickson {60] Division of Ser, No. 266 ()9l,June 26, I972 Pat, No.

3,80 l .6] l which is u cnntinuati0n-in-part of Scr4 N0. ABSTRACT 1873910 Aliphatic substituted allenic and diolefinic esters, intermediates therefor, derivatives thereof and the con- [52] U.S. Cl 0. 260/615 R; 252/56 R; 260/893;

26U/4l0; 260/601 N; 260/602; 260/884; 260/885; 260/633; 424/312; 424/314 trol of insects.

6 Claims, N0 Drawings ALKYNYL ALCOHOLS This is a division of Ser. No. 266.091. filed June 26, 1972, now US. Pat. No. 3.801.611. which is a con- R is alkyl; and

each of R' and R is hydrogen or lower alkyl.

Esters offormula (A) can be prepared as outlined below:

2 11 u l RI 0 l l l l R'" is a metal such as lithium, sodium. potassium or magnesium.

In the above outlined synthesis, an aldehyde of formula I is reacted with an alkynylide of formula II to produce the alkynyl alcohol of formula C which is then reacted with a trialkylorthoester in the presence of weak acid catalyst to yield an allenic ester of formula B. The 3,4-allene B is rearranged to the 2,4-diene A by treatment with base. Preparation of alkynyl alcohols is described by Kimel et al.. J. Org. Chem. 22, 16H 1957). The conversion of alkynyl alcohols to allenic esters is reported by Crandall et al, Chem. Commun, 141] (1970) and our application Ser. No. lll.768. filed Feb. 1. I971.

The starting material aldehydes of formula I are prepared according to the procedures described in our pending application Ser. No. [87,897, filed Oct. 8, 1971, the disclosure of which is incorporated by reference.

The compounds of formula A are useful for the control of insects. The utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect. namely. during the embryo. larvae or pupae stages in view of their effect on metamorphosis and otherwise causing abnormal development leading to death or to inability to reproduce. These conr pounds are effective control agents for Heteropte rans. such as Lygaeidae, Miridae and Pyrrhocoridae; Hornopterans, such as Aphididae. Coccidae and Jassidae; Lepidopterans, such as Pyralidae. Noctuidae and Gelcchiidae; Coleopterans, such as Tenebrionidae,

Crysomelidae and Dermestidae; Dipterans, such as Culicidae, Muscidae and Sarcophagidae', and other insects. The compounds can be applied at low dosage levels of the order of 0.01 ug. to 10 pg. per insect. Suitable carricr substances include liquid or solid inert carriers, such as water, acetone. xylene, mineral or vegetable oils, talc, vermiculite. natural and synthetic resins and silica. Treatment of insects in accordance with the present invention can be accomplished by spraying.

dusting or otherwise contacting the insect, directly or indirectly, with one or more compounds of formula A. Generally, a concentration of less than 257r of the active compound is employed. The fomiulations can include insect attractants. emulsifying agents or wetting agents to assist in the application and effectiveness of the active ingredient.

In addition to the compounds of formula A having activity useful for the control of insects. the compounds of formula A have numerous other useful applications. For example, the esters of formula A and the allenic esters of formula B of the present invention are useful lubricants and plasticizers for polymers, such as SBR. polybutadiene. ethylene-propylene copolymers and polypropylene and aid in the processing and application of polymers.

The term "alkyl", as used herein, refers to a straight or branched chain saturated aliphatic hydrocarbon group having a chain length of one to twelve carbon atoms, such as methyl, ethyl, n-propyl i propyl, n butyl. n-hexyl, n-amyl, n-heptyl, n-octyl. n-nonyl, lauryl, n-decyl, t-amyl, B-ethylpentyl and Z-methylhexyl.

The term lower alltyl, as used herein, refers to a straight or branched chain saturated aliphatic hydrocarbon group having a chain length of one to six carbon atoms, e.g., methyl, ethyl, propyl, i-propyl, n-butyl, s butyl, t-butyl, pentyl and hexyl.

The term lower alkoxy", as used herein refers to a branched or straight chain saturated aliphatic hydrocarbon group, having a chain length of l to 6 carbon atoms, with an oxygen atom bonded to the C-1 carbon atom, such as methoxy, ethoxy, isopropoxy and tbutoxy, preferably, lower alkoxy of one to 3 carbon atoms.

The presence of an olefinie bond at position C-2 and (-4 of the compounds of formula A gives rise to four isomers, each of which is embraced by the present invention. A mixture of isomers is suitably employed for the control of insects such as a mixture containing the trans I), trans (4) isomer and the cis (2), trans (4) isomer. The conditions of the synthesis described herein and the reactants can be selected so as to favor formation of one isomer such the all trans isomer over the formation of other isomers. The selection of appropriate conditions and reactants to favor formation of one isomer over another will be apparent to those of ordi nary skill in the art giving due consideration to the specific examples hereinafter. In the specific examples hereinafter, when isomerism is not specified, it is undcrstood to include a mixture of isomers which, if desired, can be separated using known separation methods.

The following examples are provided to illustrate the practice otthe present invention. Temperature is given in degrees Centigrade.

EXAMPLE 1 A. To magnesium propynylide 15 g.) in ISO ml. of ether is slowly added 0.3 moles of 7-methoxy 3,7- dimethyloctan-l-al, at and the mixture then stirred overnight. Saturated aqueous ammonium chloride is added and the layers separated. The organic phase, combined with ether backwashings of aqueous phase, is washed with water, dried and solvent evaporated to yield l(J-ntethoxy-o,lO-dimethylundec-2-yn-4-ol which can be purified by chromatography B. A mixture of 18.5 g. of the alkynyl alcohol of part A. 80 g. of triethylorthoacetate and ().7g. of propionic acid is refluxed under a spinning band column to remove ethanol as it is formed. After the elimination of ethanol is about complete, the crude reaction product is distilled under vacuum to yield ethyl ll-methoxy- 3,7,] l trimethyldodeca-3,4-dienoate. the crude reaction product is purified by chromatography on silica.

C. A solution of 1.0 g. of the allenic ester of part B in It) ml. of ethanol is treated with 4 ml. of aqueous 2N sodium hydroxide and left at room temperature for several minutes. The mixture is then poured into pentane and washed with saturated brine and separated. Evaporation of the organic phase yields ethyl ll-methoxy- 3,7,l l-trimethyldodecaQA-dienoatc.

EXAMPLE 2 The process of Example l, part A. is repeated using Alternatively,

each of the aldehydcs under column I as the starting material to yield the respective alkynyl alcohol under column ll. each of which is reacted with triethylorthoacetate using the process of Example 1, part B, to prepare the respective allenic ester under column Ill.

7-ethoxy-3,7-dimethylnonanl-al 7-ethoxy-3-niethyl7-ethylnonan- 1 -al 7-ethoxy-3 ,7-diethylnonan- 1 -al 8-ethoxy-4,8-dimethylnonanl-al 6-ethoxy-3 ,o-dimethylheptanl -al 6-ethoxy-3,fi-dimethyloctanl-al o-ethoxy-Z,-dimethylheptanl -al l0-ethoxy-6. l(l-dimethyldodec-2-yn-4-ol lO-ethoxy-(J-methyL lO-ethyldodec-2-yn-4-ol l()-ethoxy-6, lO-diethyldodec-2yn-4-ol l l-ethoxy-7, l l -dimethyldodec-2-yn-4-ol 9-ethoxy-6.9-dimethyldec-2-yn-4-ol 9-ethoxy-6,9-dimethylundec-2-yn-4-ol 9-ethoxy-5 ,Q-dimethyldec-2-yn-4-ol lll ethyl l l-ethoxy-3,7,l l-trimethyltrideca3,4-dienoate ethyl l-ethoxy-3,l l-dimethyl-7-ethyltrideca-3,4-

dienoate ethyl l l-ethoxy-3-methyl-7,l l-diethyltrideca-3,4-

dienoate ethyl l2-ethoxy-3,8, l 2-trimethyltrideca-3 ,4-dienoate ethyl l()-ethoxy-3,7, l()-trimethylundeca-3,4-

dienoate ethyl lU-ethoxy-3,7, l()-trimethyldodeca-3,4-

dienoate ethyl l()-ethoxy-3,6, l U-trimethylundeca-3 ,4-

dienoate Using the process of Example 1, part C, each of the allenic esters under column III is rearranged by treatment with aqueous sodium hydroxide to produce the respective a,B-unsaturated ester.

EXAMPLE 3 Following the process of part A of Example 1, magnesium acctylide is reacted with 7-isopr0p0xy-3,7- dimethyloctanl-al well the isopropoxy derivative of each of the aldehydes under column l to produce the respective alkynyl alcohol under column IV.

9-isopropoxy-5 ,Q-dimethyldec- 1 -yn3-0l )-isopropoxy-5 ,9dimethylundecl -yn-3-ol 9-isopropoxy-S-methyl-9-ethylundecl -yn-3-ol 9-isopropoxy-5 .Q-diethylundecl -yn-3-ol lU-isopropoxy-6, l 0dimethylundecl -yn-3-ol 8-isopropoxy-5 ,S-dimethylnonl -yn-3-ol 8-isopropoxy-5 ,8-dimethyldecl -yn-3ol 8-isopropoxy-4,S-dimethylnonl -yn-3-ol Each of the alkynyl alcohols under column IV is reacted with triethylorthoacetatc using the procedure of Example 1, part B, to prepare the respective allenic ester under column V.

ethyl l l-isopropoxy-7. l l-dimethyldodeca-3,4-

dienoate ethyl l l-isopropoxy-7.l l-dimethyltrideca-3.4-

dienoate ethyl l l-isopropoxy-7-ethyl-l l-methyltrideca-3.4-

dienoate ethyl l l-isopropoxy-7.l l-diethyltridecal ldienoate ethyl l2-isopropoxy-8,12-dimethyltrideca-3,4-

dienoate ethyl lU-isopropoxy-7, lU-dimethyIundeca-3 .4

dienoate ethyl lO-isopropoxy-7. l()-dimethyldodeca-3,4

dienoate ethyl lO-isopropoxy-6, lU-dimethylundeca-3 ,4-

dienoate Each of the allenic esters under column V is rearranged by treatement with aqueous sodium hydroxide to prepare the respective a,B-unsaturated ester.

EXAMPLE 4 A. To magnesium propynylide (g) in ISO ml. of ether is slowly added 0.3 moles of 7-hydroxy-3,7- dimethyll -octanal and the mixture stirred overnight at 0. Saturated aqueous ammonium chloride is added and the layers separated. The organic phase, combined with ether backwashings of aqueous phase. is washed with water, dried and solvent evaporated to yield I0- hydroxy-.lO-dimethylundec-2-yn-4-ol which can be purified by distillation or chromatography.

B. A mixture of l8.5 g. of l()-hydroxy-6,l()- dimethylundec-2-yn-4-ol. 80 g. of triethylorthoacetate and 0.75 g. of propionic acid is refluxed under a spinning band column to remove ethanol as it is formed. After the elimination of ethanol is about complete, the crude reaction product is distilled under vacuum to yield ethyl l lhydroxy-3.7,l l-trimethyldodeca-3,4- dienoate. Alternatively, the crude reaction product is purified by chromatography on silica.

C. A solution of l.() g. of the allenic ester of part B in ml. of ethanol is treated with 4 ml. of aqueous 2N sodium hydroxide and left at room temperature for sev eral minutes. The mixture is then poured into pentane and washed with saturated brine and separated. Evaporation of the organic phase yields ethyl ll-hydroxy 3.7.1 l-trimethyldodeca-Z.4-dienoate.

EXAMPLE 5 The process of part A of Example 4 is repeated using each of the aldehydes under column VI to produce the respective alkynyl alcohol under column VII.

7fluoro-3,7-dimethylnonanl -a] 7-fluoro-3.7-dimethyloctanl -al S-fluoro-lS-dimethylhexanl -al 6-fluoro-3.o-dimethylheptam l -al VI I ltl-fluoro-o, l(l-dimethylundec-2-yn4-ol The alkynyl alcohols under column VII are reacted with triethylorthoacetate to produce the respective allenie ester under column VIII which are rearranged ro produce the respective mB-unsaturated estersv VIII ethyl l l-fluoro-3.7,l l-trimethyltrideca-3.4-dienoate ethyl l l-fluoro-3.7.l l-trimethyldodeca3.4-dienoate ethyl 9-fluoro-3,6.9-trimethyldeca-3,4dienoate ethyl lO-fluoro-3,7.lO-trimethylundeca-3,4-dienoate EXAMPLE 6 Following the procedure of Example 4 (A) sodium acetylide is reacted with each of the chloro derivatives of the aldehydes under column VI to produce the respective alkynyl alcohol under column IX.

9-chloro-5,Q-dimethylundecl -yn-3-ol 9-chloro-5 ,Q-dimethyldecl -yn-3-ol 7-chloro-4,7-dimethyloct- I -yn- 3-ol 8-chloro-5,8-dimethylnonl -yn 3-0] Each of the alkynyl alcohols under column IX is then reacted with triethylorthoacetate to produce the respective allenic ester under column X which are rearranged to produce the respective 2,4-dienoate.

ethyl l l-chlor0-7,l l-dimethyltrideca-3.4-dienoate ethyl l l-chloro-7,l l-dimethyldodeca-3,4-dienoate ethyl 9-chloro-6,9-dimethyldeca-3,4-dienoate ethyl lO-chIoro-7.lOdimethylundeca-FrA-dienoate The use of trimethylorthoacetate in the foregoing ex amples in place of triethylorthoacetate produces the corresponding methyl esters.

EXAMPLE 7 A. To 46 g. of lithium propynylide in 700 ml. of dimethylformamide, cooled in an ice-bath, is added a solution of 60 g. of 7-methoxy-3.7-dimethyloctanl al in 300 ml. of dimethylformamide over a period of 3 hours. The mixture is stirred at room temperature overnight. The reaction is worked up by adding SUU ml. of saturated aqueous ammonium chloride and extracting with ether. The organic phase is washed well with water, dried over calcium sulfate and the solvent is evaporated at reduced pressure to yield l0methoxy-6 l()- dimethylundec-2-yn-4-ol. which can be purified by distillation.

B. A mixture ofZ g. of the alkynyl alcohol of Part A, l l.5 ml. of triethylorthoacetate and 0.05 g. of propi onic acid is heated to l20l 30 under a spinning band column for about 3 hours. The crude reaction product is then distilled under vacuum to give ethyl l lmethoxy-3,7,l l-trimethyldodeca-3.4-dienoate.

C. To mg. of the allenic ester of Part B in 10 ml. of dimethylformamide. at l5, is added 20 mg. of so dium ethoxide. The mixture is left at room temperature for 2 days. Water and ether is added and the organic layer separated, washed with brine, dried and evaporated to yield ethyl l l-methoxy 3.7,l l-trimethyldodeca-2,4-dienoate.

By use of tri-isopropylorthoacetate in place of triethylorthoacctate in Part B, there is obtained the isopropyl allenic ester which upon rearrangement with the basic treatment of Part C. affords isopropyl l lmethoxy-3,7.l l-trimethyldodeca-2. l-dienoate.

EXAMPLE 8 Five grams of 7-hydroxy-3,7-dimethyloctan-l-al are processed as described in Example 7, Parts A and B, to

give lU-hydroxy-o, l ()-dimethylundec-2-yn-4-ol and ethyl l l-hydroxy-3.7.l l-trimethyldodcca-3,4-dienoate successively.

To the allenic ester thus-prepared (500 mg.) in ll) ml. of ethanol is added 5 ml. ofa 40% methanolic solu tion of N-henzyltrimcthylammonium hydroxide (Triton B) and the mixture is allowed to stand at room temperature for 5 hours. The reaction is worked up as in Part C of Example 7 to yield ethyl l l-hydroxy-3,7.l ltrimethyldodeca-2.4-dienoate.

Substituting triethylorthoacetate by each of trimethylorthoacetate and tri-isopropylorthoacetate yields the corresponding methyl and isopropyl allenic esters which are ultimately converted into the respective methyl and isopropyl 2,4-dienoatesv What is claimed is: l. A compound selected from those of the following formula: 

1. A COMPOUND SELECTED FROM THOSE OF THE FOLLOWING FORMULA:
 2. A compound according to claim 1 wherein n is one and Z is methoxy or ethoxy.
 3. The compound, 10-methoxy-6,10-dimethylundec-2-yn-4-ol, according to claim
 1. 4. The compound, 10-ethoxy-6,10-dimethyldodec-2-yn-4-ol, according to claim
 1. 5. The compound, 9-ethoxy-6,9-dimethyldec-2-yn-4-ol, according to claim
 1. 6. The compound, 9-ethoxy-6,9-dimethylundec-2-yn-4-ol, according to claim
 1. 